EP2986591B1 - Verfahren zur herstellung von nitrilen unter verwendung eines katalysators aus antimon und eisen - Google Patents
Verfahren zur herstellung von nitrilen unter verwendung eines katalysators aus antimon und eisen Download PDFInfo
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- EP2986591B1 EP2986591B1 EP14725224.1A EP14725224A EP2986591B1 EP 2986591 B1 EP2986591 B1 EP 2986591B1 EP 14725224 A EP14725224 A EP 14725224A EP 2986591 B1 EP2986591 B1 EP 2986591B1
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- 239000003054 catalyst Substances 0.000 title claims description 36
- 150000002825 nitriles Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 15
- 229910052742 iron Inorganic materials 0.000 title description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title description 4
- 229910052787 antimony Inorganic materials 0.000 title description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 33
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011949 solid catalyst Substances 0.000 claims description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 14
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XUGISPSHIFXEHZ-GPJXBBLFSA-N [(3r,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-GPJXBBLFSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to the use of an antimony and iron catalyst to catalyze the production of nitriles, especially acrylonitrile, and to a process for the production of nitriles, especially acrylonitrile, in gas phase, in the presence of such a catalyst.
- textile fibers such as acrylic fibers, nylon, synthetic rubber, or else nitrogen elastomers after copolymerization with butadiene, or even high performance solid resins (acrylonitrile butadiene styrene: ABS resins) after copolymerization with butadiene and styrene.
- ABS resins high performance solid resins
- This reaction is carried out in the gas phase in a fluidized bed reactor, at high temperature, generally at 350-400 ° C., in the absence of water and in the presence of a catalyst based on bismuth and molybdenum.
- the use of the catalyst of formula (I) above makes it possible to carry out the ammoxidation reaction of an alcohol of formula (II) to give a nitrile of formula (III), corresponding, in particular to acrylonitrile, in the gas phase with a very good performance.
- This reaction also makes it possible, by way of byproducts, to access acrolein (and acrylic acid by subsequent oxidation of acrolein), acetone, acetaldehyde, acetonitrile and propionaldehyde, which are also valuable because they are intermediaries widely used in the chemical industry.
- the raw material (the alcohol of formula (II)) can be produced from renewable resources, which makes it possible to dispense with the fossil resources to access the nitriles of formula (III), and in particular acrylonitrile.
- glycerol alone or in admixture with formic acid, may be used to produce allyl alcohol according to various gas phase or liquid phase catalytic processes described in the literature, particularly in international applications. WO 2008/092115 and WO 2011/08509 .
- the catalyst of formula (I) above may especially be prepared according to the method described by Allen MD et al. (Catalysis Letters 33, 1995, 269 ) or by Li K.-T. et al. (Applied Catalysis A: General 156, 1997, 117-130 ). Briefly, this process involves reacting an acidic aqueous solution an iron salt, such as, for example, iron nitrate, at a temperature of about 80 ° C., with antimony oxide (Sb 2 O 3 ) and then maintaining the temperature between 80 and 90 ° C. for several hours to evaporate the solvent and obtain a pasty product which is then dried at about 100 ° C for several days. The resulting catalyst powder is then pressed into pellets which are then ground into a powder which is preferably calcined under static air for at least 30 minutes at a temperature preferably between 300 and 700 ° C.
- an iron salt such as, for example, iron nitrate
- a solid catalyst selected from the following compounds of formula (I): Sb x Fe 1 O y (I) where x varies
- the separation of the co-products of the reaction can be carried out according to techniques known to those skilled in the art and these co-products can also be valued because they are intermediates of interest in the chemical industry.
- R 1 represents a hydrogen atom
- the alcohol of formula (II) is allylic alcohol and the nitrile of formula (III), acrylonitrile.
- R 1 is a methyl radical
- the alcohol of formula (II) is methallyl alcohol and the nitrile of formula (III) is methacrylonitrile.
- R 1 represents a hydrogen atom.
- the process according to the invention comprises a step of ammoxidation of allyl alcohol acrylonitrile.
- the catalyst is preferably chosen from compounds of formula (I) in which x varies from 0.5 to 0.8 inclusive.
- the ammoxidation reaction is preferably carried out at a temperature greater than or equal to about 400 ° C., and even more preferably at a temperature ranging from about 350 to 450 ° C. inclusive.
- the ammoxidation reaction is carried out at atmospheric pressure.
- the contact time defined as the ratio between the volume of catalyst (in mL) and the total volume flow rate of the gas injected into the reactor (in mL / s), calculated at the temperature and the pressure of the reaction, varies preferably from about 0.05 to 2 s, and still more preferably from about 0.05 to 0.5 s.
- the molar alcohol ratio of formula (II) / ammonia may vary from 1/1 to about 1/4. According to a preferred embodiment of the invention, the ammoxidation reaction is conducted using a gas phase in which the molar ratio alcohol of formula (II) / ammonia is equal to about 1/3.
- the molar alcohol ratio of formula (II) / oxygen may vary from 1 / 1.5 to about 1/5.
- the ammoxidation reaction is conducted using a gas phase in which the molar ratio alcohol of formula (II) / oxygen is equal to about 1 / 3.5.
- the ammoxidation reaction is conducted using a gas phase in which the molar ratio alcohol of formula (II) / oxygen / ammonia is about 1 / 3.5 / 3.
- the catalyst of formula (I) can be supported by a porous solid support.
- the porous solid support may be chosen from silica-based supports, in particular in the form of silica gel (CARiACT® type), of mesostructured silica (for example silica mesostructured type SBA-15), as well as among supports based on mixed silica oxides such as for example SiO 2 -TiO 2 , SiO 2 -ZrO 2 ; and supports made of silicon carbide (SiC), etc.
- Such a porous solid support preferably has a mean porosity of between 0.1 cm 3 / g and 2.0 cm 3 / g inclusive, and even more preferentially between 0.5 cm 3 / g and 1.5 cm 3 / g inclusive.
- the separation of the coproducts from the reaction can be carried out by any appropriate techniques known to those skilled in the art, for example by distillation.
- the present invention is illustrated by the following exemplary embodiments, to which it is however not limited.
- the value of y for each of these catalysts is determined by the respect of the electro-neutrality and / or the valences of the elements. It has not been measured experimentally.
- the synthesis of acrylonitrile was carried out in the gas phase in a fixed-bed tubular reactor with a diameter of 15 mm and a length of 120 mm.
- the temperature of the reactor was precisely regulated and controlled by a thermocouple.
- a 0.05M solution was prepared by dissolving 2.21 g of oxalic acid in 500 mL of water at 80 ° C with stirring. After dissolution was complete, 140.97 g of non-hydrated iron nitrate was added to the oxalic acid solution maintaining the temperature at 80 ° C. After complete dissolution of iron nitrate non-hydrated, 30.51 g of antimony (III) oxide was added. The resulting solution was evaporated maintaining the temperature at 80 ° C with stirring until a viscous solution was obtained which was then oven-dried at 120 ° C for 72 hours. After drying, the product obtained was pressed into pellets which were then milled to obtain a powder product composed of particles having a size of between 250 and 630 ⁇ m.
- a catalyst of formula (I) in which x 1.0 was prepared according to a procedure identical to that of Example 1 above but using 2.21 g of oxalic acid, 22.2 g of nitrate of non-hydrated iron and 8.0 g of antimony (III) oxide.
- the products resulting from the reaction were analyzed after trapping at the reactor outlet in a bubbler maintained at low temperature (-4 ° C.). The resulting liquid was then analyzed on a gas chromatograph equipped with a flame ionization detector.
- the ammoxidation reaction of the allyl alcohol was carried out according to the method detailed in Example 5 above under operating conditions allowing the total conversion of the allyl alcohol, using the catalyst prepared according to the invention.
- Example 1 at a temperature of 400 or 450 ° C, and using different molar ratios of allyl alcohol / NH 3 .
- the reaction time was 5 hours.
- Example 5 the products resulting from the reaction were analyzed after trapping at the reactor outlet in a bubbler maintained at low temperature (-4 ° C.). The resulting liquid is then analyzed on gas chromatography equipped with a flame ionization detector.
- Test 8 carried out at 450 ° C. with a contact time of 0.1 s and a molar ratio of allylic alcohol. / NH 3 of 1/3. An 83% yield of acrylonitrile with a total conversion of allyl alcohol is then obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (11)
- Verwendung einer Verbindung mit der folgenden Formel (I):
SbxFe1Oy (I)
wobei x von 0,4 bis einschließlich 1 variiert und y von 1,6 bis einschließlich 4 variiert, als Katalysator, um die Ammonoxidationsreaktion eines Alkohols mit der folgenden Formel (II) zu katalysieren: CH2=C(R1)-CH2-OH (II), wobei R1 ein Wasserstoffatom oder ein Methylradikal in einem Nitril der folgenden Formel darstellt: CH2=C(R1)-C≡C (III), wobei R1 die gleiche Bedeutung wie in der Formel (II) unten aufweist, wobei die Reaktion in der Gasphase durchgeführt wird, wobei die Gasphase mindestens Sauerstoff und Ammoniak umfasst. - Verfahren zur Herstellung eines Nitrils ausgehend von einem Alkohol in Anwesenheit eines Katalysators, dadurch gekennzeichnet, dass es einen Schritt des Ammoxidierens eines Alkohols mit der folgenden Formel (II) umfasst:
CH2=C(R1)-CH2-OH (II)
wobei R1 ein Wasserstoffatom oder ein Methylradikal umfasst, um zu einem Nitril der folgenden Formel (III) zu gelangen:
CH2=C(R1)-C≡N (III);
wobei R1 die gleiche Bedeutung wie in der Formel (II) unten aufweist,
wobei die Reaktion in der Gasphase durchgeführt wird, wobei die Gasphase mindestens Ammoniak und Sauerstoff umfasst, und in Anwesenheit eines festen Katalysators, ausgewählt aus den Verbindungen mit der folgenden Formel (I):
SbxFe1Oy (I)
wobei x von 0,4 bis einschließlich 1 variiert und y von 1,6 bis einschließlich 4 variiert. - Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass R1 ein Wasserstoffatom darstellt und dadurch, dass es einen Schritt des Ammoxydierens des Allylalkohols zu Acrylonitril umfasst.
- Verfahren nach Anspruch 2 oder 3, dadurch gekennzeichnet, dass der Katalysator ausgewählt ist aus den Verbindungen, in denen x von 0,5 bis einschließlich 0,8 variiert.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass die Verbindung der Formel (I) ausgewählt ist aus den Verbindungen, in denen x = 0,6.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass die Ammoxidationsreaktion bei einer Temperatur durchgeführt wird, die von 350 bis 450 °C variiert.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 6, dadurch gekennzeichnet, dass das Verhältnis zwischen dem Katalysatorvolumen und dem gesamten Volumendurchsatz von Gas, das in den Reaktor injiziert ist, berechnet bei der Temperatur und bei dem Druck der Reaktion, von 0,05 bis 2s variiert.
- Verfahren nach einem der vorhergehenden Ansprüche 2 bis 7, dadurch gekennzeichnet, dass innerhalb der Gasphase das Molverhältnis Alkohol mit der Formel (II)/Ammoniak von 1/1 bis 1/4 variiert.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 8, dadurch gekennzeichnet, dass innerhalb der Gasphase das Molverhältnis Alkohol mit der Formel (II)/Sauerstoff von 1/1,5 bis 1/5 variiert.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 9, dadurch gekennzeichnet, dass die Amoxidationsreaktion unter Verwendung einer Gasphase durchgeführt wird, in der das Molverhältnis Alkohol mit der Formel (II)/Sauerstoff 1/3, 5/3 ist.
- Verfahren nach einem beliebigen der Ansprüche 2 bis 10, dadurch gekennzeichnet, dass der Katalysator mit der Formel (I) durch einen festen porösen Träger getragen wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1353478A FR3004713B1 (fr) | 2013-04-17 | 2013-04-17 | Procede de production de nitriles mettant en oeuvre un catalyseur a base d'antimoine et de fer. |
PCT/FR2014/050924 WO2014170604A1 (fr) | 2013-04-17 | 2014-04-16 | Procede de production de nitriles mettant en œuvre un catalyseur a base d'antimoine et de fer |
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EP2986591A1 EP2986591A1 (de) | 2016-02-24 |
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US (1) | US9676705B2 (de) |
EP (1) | EP2986591B1 (de) |
JP (1) | JP6382942B2 (de) |
CN (1) | CN105308019B (de) |
FR (1) | FR3004713B1 (de) |
WO (1) | WO2014170604A1 (de) |
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EP3608305A1 (de) | 2018-08-10 | 2020-02-12 | Röhm GmbH | Verfahren zur herstellung von methacrylsäure oder methacrylsäureestern |
WO2020048852A1 (en) * | 2018-09-07 | 2020-03-12 | Basf Se | Process for the preparation of alpha, beta unsaturated aldehydes by oxidation of alcohols in the presence of a liquid phase |
CN113828337B (zh) * | 2020-06-24 | 2024-02-02 | 中国石油化工股份有限公司 | 丙烯氨氧化制丙烯腈催化剂及其制备方法和应用 |
CN113559904B (zh) * | 2021-07-16 | 2024-04-02 | 南京理工大学 | 氮碳材料锚定的铁单原子催化剂在催化醇的氨氧化制腈反应中的应用 |
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GB709337A (en) | 1950-12-30 | 1954-05-19 | Distillers Co Yeast Ltd | Manufacture of nitriles |
BE633452A (de) * | 1962-06-11 | |||
JPS5846054A (ja) * | 1981-09-11 | 1983-03-17 | Asahi Chem Ind Co Ltd | メタクリロニトリルを製造する方法 |
GB2302291B (en) * | 1995-06-15 | 1999-07-07 | Basf Plc | Ammoxidation of propane and preparation of catalyst therefor |
US6458742B1 (en) * | 2000-08-17 | 2002-10-01 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile |
WO2008092115A1 (en) | 2007-01-26 | 2008-07-31 | The Regents Of The University Of California | Conversion of glycerol from biodiesel production to allyl alcohol |
ES2319949B1 (es) * | 2007-11-13 | 2010-03-17 | Consejo Superior De Investigaciones Cientificas | Proceso catalitico de produccion de nitrilos a partir de alcoholes. |
JP5011176B2 (ja) * | 2008-03-14 | 2012-08-29 | ダイヤニトリックス株式会社 | アクリロニトリル合成用触媒およびアクリロニトリルの製造方法 |
RU2495720C2 (ru) * | 2008-08-01 | 2013-10-20 | ИНЕОС ЮЭсЭй ЭлЭлСи | Способ приготовления смешанных металлоксидных катализаторов окислительного аммонолиза и/или окисления низших алканов |
US8357621B2 (en) | 2009-06-29 | 2013-01-22 | E.I. Du Pont De Nemours And Company | Soil resist method |
CN102010350B (zh) * | 2009-09-07 | 2013-12-18 | 中国石油化工集团公司 | 增加丙烯腈或甲基丙烯腈生产能力的方法 |
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2013
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2014
- 2014-04-16 JP JP2016508219A patent/JP6382942B2/ja active Active
- 2014-04-16 WO PCT/FR2014/050924 patent/WO2014170604A1/fr active Application Filing
- 2014-04-16 EP EP14725224.1A patent/EP2986591B1/de active Active
- 2014-04-16 CN CN201480021126.5A patent/CN105308019B/zh active Active
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US9676705B2 (en) | 2017-06-13 |
US20160023995A1 (en) | 2016-01-28 |
FR3004713B1 (fr) | 2015-05-15 |
FR3004713A1 (fr) | 2014-10-24 |
CN105308019B (zh) | 2018-02-06 |
JP6382942B2 (ja) | 2018-08-29 |
WO2014170604A1 (fr) | 2014-10-23 |
JP2016516803A (ja) | 2016-06-09 |
CN105308019A (zh) | 2016-02-03 |
EP2986591A1 (de) | 2016-02-24 |
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